Organic acid removal from liquid hydrocarbon product streams

ABSTRACT

Systems and processes for removing organic acids from liquid hydrocarbon product streams are provided. The systems and processes can include injecting an ammoniated water wash into a liquid hydrocarbon product stream, such as an effluent stream from a methanol conversion process, and subsequently separating the treated liquid hydrocarbon product stream from the wash water. The addition of ammonia can reduce the amount of water wash by an unexpected amount.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/796,167, filed on Jan. 24, 2019, the entire contents of which areincorporated herein by reference.

FIELD

Systems and processes for removing organic acids from liquid hydrocarbonproducts streams are disclosed.

BACKGROUND

Various industrial processes are utilized for the conversion of lowboiling carbon-containing compounds to higher value products. Forexample, the commercial methanol-to-gasoline (MTG) process producesgasoline from methanol using ZSM-5 catalysts. In the MTG process,methanol is first dehydrated to dimethyl ether. The methanol and/ordimethyl ether then react in a series of reactions that result information of aromatic, paraffinic, and olefinic compounds. The resultingproduct includes liquefied petroleum gas (LPG) and a high-qualitygasoline comprised of aromatics, paraffins, and olefins. However, incertain conventional processes the liquid hydrocarbon products caninclude small amounts of organic acids that can cause corrosion ofprocessing equipment, which can lead to costly repairs and plantdowntime. It would be desirable to mitigate the corrosive effect of theorganic acids in the MTG process or other oxygenate conversionprocesses.

SUMMARY

In various aspects, a method for removing organic acids from a liquidhydrocarbon product stream is provided. The method can include exposinga liquid hydrocarbon product stream comprising naphtha boiling rangecompounds, light ends, and 1 ppmw or more of organic acids to a waterwash stream comprising ammonia to form a treated liquid hydrocarbonproduct stream. The amount of the water wash stream can be 0.5 L to 20 Lper barrel of the liquid hydrocarbon product stream. The water wash caninclude a) 4.0 g or more of ammonia per barrel of the liquid hydrocarbonproduct stream, b) a ratio of moles of ammonia in the water wash tomoles of the organic acids in the liquid hydrocarbon product stream is1.5 or more, or c) a combination of a) and b).

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts an example system for removal of organic acids fromliquid hydrocarbon product streams.

FIG. 2 depicts a graph showing estimated organic acid removal efficiencyfrom a deethanizer feed with five pounds per hour of ammonia in a waterwash stream at various rates.

FIG. 3 depicts a graph showing estimated organic acid removal efficiencyfrom a deethanizer feed with seven pounds per hour of ammonia in a waterwash stream at various rates.

FIG. 4 depicts a graph showing estimated organic acid removal efficiencyfrom a deethanizer feed with ten pounds per hour of ammonia in a waterwash stream at various rates.

FIG. 5 depicts a graph showing estimated organic acid removal efficiencyfrom a deethanizer feed with twelve pounds per hour of ammonia in awater wash stream at various rates.

DETAILED DESCRIPTION

Overview

In various aspects, systems and processes for removing organic acidsfrom liquid hydrocarbon product streams are provided. In aspects, thesystem can include injecting an ammoniated water wash into a liquidhydrocarbon product stream and subsequently separating the treatedliquid hydrocarbon product stream from the wash water. The treatedliquid hydrocarbon product stream can then be utilized in any convenientmanner, such as separation of a desired gasoline product from aremaining portion of the treated liquid hydrocarbon product.

Certain conventional processes can be utilized for converting oxygenatesinto hydrocarbon products, such as the MTG process. In certainconventional MTG processes, once the methanol is converted to the liquidhydrocarbon product a series of downstream processes are utilized toremove excess water and/or other undesirable conversion products, suchas durene (1,2,4,5, tetra-methyl benzene). In such conventional systems,the liquid hydrocarbon product may first be separated from the water ina conventional product separator. The resultant separated liquidhydrocarbon product contains naphtha boiling range compounds and lightends, in addition to small amounts of water, dissolved hydrogen, andother light gases. In conventional systems, the separated liquidhydrocarbon product is sent to a de-ethanizer for removal of at least aportion of the C²⁻ compounds (two carbon atoms or less) from the C₃₊compounds (three carbon atoms or more, such as the naphtha boiling rangecompounds). The C₃₊ effluent from the de-ethanizer can then be subjectedto a stabilizer to separate the C₃-C₄ compounds from the naphtha boilingrange compounds. In such systems, the naphtha boiling range compoundsare then subjected to a splitter where a light and heavy fraction isseparated. The heavy fraction is subjected to hydrotreatment to removethe durene or other undesirable large compounds, and may then be mixedwith the light fraction for further processing of naphtha boiling rangecompounds into gasoline. Conventional MTG processes are described inU.S. Pat. No. 4,482,772.

In certain conventional systems, the resulting liquid hydrocarbonproduct from the MTG process can include organic acids in amountssufficient to cause corrosion when in contact with stagnant water, whichdepending upon system design, may be at one or more locations within thedownstream MTG system. In one example, corrosion may occur where thelight fraction from the splitter is stored. Such corrosion can bedetrimental to the MTG systems and downstream refinery processes.Therefore, there is a need to mitigate the corrosion issues that arisefrom the organic acids present in the liquid hydrocarbon product.

As noted above, in certain systems, the corrosion can occur where thelight fraction of naphtha boiling range compounds is stored. However,treating this downstream light fraction may result in water saturationof the gasoline product, which could present haze problems in coldweather thereby requiring additional drying facilities. Further,treating the downstream light fraction of naphtha boiling rangecompounds would not prevent any potential corrosion on upstream MTGconversion or product separation systems. While the liquid hydrocarbonproduct exiting the upstream conversion product separator may besubjected to a water wash in an attempt to remove the organic acids, thevolumes of water required to remove substantial amounts of the organicacids would be too resource intensive to process in conventionalsystems.

The systems and processes described herein solve one or more theabove-mentioned problems related to the presence of organic acids in anMTG conversion product. It has been discovered that addition of ammoniato a water wash stream for washing of the liquid hydrocarbon productupstream of the de-ethanizer allow for an unexpectedly large reductionin the amount of water that is needed for effective removal of organicacids. Without being bound by any particular theory, it is believed thatat least a portion of the organic acids are solvated within the liquidhydrocarbon product, and as a result cannot be easily transferred to aneutral aqueous phase. Addition of a weak base, such as ammonia, canallow water wash to act as an extraction, so that the organic acids canbe efficiently transferred to the aqueous phase corresponding to thewater wash. By improving the ability to transfer the organic acids fromthe hydrocarbon phase to the aqueous phase, the amount of water requiredto achieve a desired level of organic acid removal can be reduced by anunexpectedly large amount. As shown below, the reduction in volume ofwater can correspond to a reduction by an order of magnitude or more.

For example, in certain aspects, exposing a liquid hydrocarbon productstream to ammonia in an amount of 4.0 g or more of ammonia (in anaqueous solution) per barrel of the liquid hydrocarbon product streamcan significantly reduce the organic acids present therein. With regardto the water wash, the volume of the water wash stream containing theammonia can correspond to 0.5 L or more of water wash per barrel of theliquid hydrocarbon product stream (or 2.0 L or more). As discussedbelow, in certain aspects, the aforementioned small amounts of ammoniareduce the water wash amount over at least one order of magnitudecompared to the amounts required to remove organic acids in the absenceof the ammonia. Further, the processes described below can includemonitoring the pH of the separated water wash stream in order to ensurethe appropriate amount of organic acids are being removed from theliquid hydrocarbon product.

In this discussion, the “naphtha boiling range” is defined as 50° F.(−10° C., roughly corresponding to the lowest boiling point of a pentaneisomer) to roughly 437° F. (−225° C.). Thus, the phrase “naphtha boilingrange compounds” refers to one or more compounds having boiling pointsin the naphtha boiling range. Further, in this discussion, “light ends”refers to hydrocarbon compounds that exhibit a boiling range below thenaphtha boiling range described above. It is noted that due to practicalconsideration during fractionation (or other boiling point basedseparation) of hydrocarbon-like fractions, a fuel fraction formedaccording to the methods described herein may have T5 and T95distillation points corresponding to the above values (or T10 and T90distillation points), as opposed to having initial/final boiling pointscorresponding to the above values. While various methods are availablefor determining boiling point information for a given sample, for theclaims below ASTM D86 is a suitable method for determining distillationpoints (including fractional weight distillation points) for acomposition.

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Processes for Organic Acid Removal from Liquid Hydrocarbon ProductStreams

As discussed above, in various aspects, processes for the removal oforganic acids from liquid hydrocarbon product streams are described. Inaspects, the liquid hydrocarbon product stream can be an effluent froman oxygenate conversion process, such as the MTG process describedabove. In various aspects, the liquid hydrocarbon product stream caninclude naphtha boiling range compounds, light ends, organic acids,small amounts of water, or a combination thereof. In certain aspects,the naphtha boiling range compounds present in the liquid hydrocarbonproduct stream can exhibit a Research Octane Number (RON) of 70 or more,or 80 or more, or 90 or more, such as up to 110 or possibly stillhigher. The Research Octane Number (RON) can be determined according toASTM D2699. In aspects, small amounts of water can be present in theliquid hydrocarbon product stream prior to the water washing, such aswater in an amount of 10 ppm to 3000 ppm, or 200 ppm to 2000 ppm. Insome aspects, the liquid hydrocarbon product stream can be ade-ethanizer feed. As used herein, a de-ethanizer feed refers to aliquid hydrocarbon product stream from a MTG conversion process that isintended to be subjected to a de-ethanizer for removal of C²⁻hydrocarbons.

The organic acids present in the liquid hydrocarbon product stream caninclude any organic acids produced from the conversion of oxygenates toa liquid hydrocarbon product stream. In some aspects, the organic acidscan include acids having six carbon atoms or less, or five carbon atomsor less. For example, the organic acids can include formic acid, aceticacid, propionic acid, butyric acid, or combinations thereof. In certainaspects, collectively, the organic acids can be present in the liquidhydrocarbon product stream in an amount of 1 ppmw to 700 ppmw, or 5 ppmwto 500 ppmw, or 10 ppmw to 300 ppmw, or 50 ppmw to 700 ppmw, or 50 ppmwto 500 ppmw. It should be understood that the relative amount of organicacids and the specific types of organic acids present in a liquidhydrocarbon product stream can vary based on the upstream oxygenateconversion processes utilized.

In certain aspects, the ammoniated water wash stream can include ammoniain any amount. In certain aspects, the ammonia is present in an amountthat is a molar equivalent or molar excess of the amount of organicacids present in the liquid hydrocarbon product stream. In one aspect,the ratio of moles of ammonia to moles of organic acids can be 1.0 ormore, or 1.5 or more, or 1.8 or more, or 2.0 or more, or 3.0 or more, or4.0 or more, such as up to 10 or possibly still higher.

In various aspects, ammonia can be present in an amount of 4.0 g or moreper barrel of liquid hydrocarbon product stream, or 5.0 g or more, or5.5 g or more, or 7.5 g or more, or 10 g or more, such as up to 50 g orpossibly still higher. In aspects, the ammonia can be present in anamount of 4.5 g to 50 g per barrel of liquid hydrocarbon product stream,5.5 g to 40 g per barrel of liquid hydrocarbon product stream, or 7.5 gto 35 g per barrel of liquid hydrocarbon product stream.

In various aspects, the water in the ammoniated water wash stream ispresent in an amount of 20 liters (L) or less per barrel of liquidhydrocarbon product stream, 15 L or less per barrel of liquidhydrocarbon product stream, or 10 L or less per barrel of liquidhydrocarbon product stream. In the same or alterative aspects, the waterin the ammoniated water wash stream is present in an amount of 0.5liters (L) or more per barrel of liquid hydrocarbon product stream, 2.0L or more per barrel of liquid hydrocarbon product stream, or 3.5 L ormore per barrel of liquid hydrocarbon product stream. In certainaspects, the water in the ammoniated water wash stream is present in anamount of 0.5 L to 20 L per barrel of liquid hydrocarbon product stream,2.0 L to 15 L per barrel of liquid hydrocarbon product stream, or 2.0 Lto 10 L per barrel of liquid hydrocarbon product stream.

In certain aspects, the ammonia and water are housed separately and theammonia can be injected into the water wash stream prior to contact withthe liquid hydrocarbon product stream. In such aspects, the ammonia andwater can be arranged and housed in any convenient manner that can beused in refinery systems.

As discussed above, in certain aspects, the liquid hydrocarbon productstream, e.g., a de-ethanizer feed, is exposed to the ammoniated waterwash stream upstream of a de-ethanizer. In such aspects, the ammoniatedwater wash stream may be injected into the liquid hydrocarbon productstream using any devices or processes convenient for use in a refinerysetting. For instance, in one aspect, the ammoniated water wash may bespray injected into the liquid hydrocarbon product stream in such amanner so as to maximize intermixing. In one aspect, the liquidhydrocarbon product stream is exposed to the ammoniated water washstream in a deethanizer feed conduit in fluid communication with adeethanizer.

In aspects, after exposure of the ammoniated water wash stream, theliquid hydrocarbon product stream can be separated from the water washstream. In such aspects, the water wash and liquid hydrocarbon productcan be separated using any technique that is convenient in a refinerysetting, such as a coalescer. In such aspects, the water stream exitsthe coalescer and can be treated and/or re-used as a water wash stream,while the treated liquid hydrocarbon product stream separately exits thecoalescer and can then proceed for downstream processing, such as with ade-ethanizer. In one or more aspects, the pH of the separated water washstream can be 5.5 or more, 6 or more, or 7 or more, such as up to 9.0 orpossibly still higher.

In certain aspects, 80% or more, or 90% or more, or 95% or more, or 99%or more of the organic acids that were present in the liquid hydrocarbonproduct stream can be removed by the ammoniated water wash andsubsequent separation of the water wash stream from the treated liquidhydrocarbon product stream. In certain aspects, 80% or more, or 90% ormore, or 95% or more, or 99% or more of the acetic acid, propionic acid,butyric acid, formic acid, or a combination thereof that was present inthe liquid hydrocarbon product stream can be removed by the ammoniatedwater wash and subsequent separation of the water wash stream from thetreated liquid hydrocarbon product stream.

As discussed above, in certain aspects, the pH of the water wash exitingthe coalescer can be monitored in order to ensure effective organic acidremoval from the liquid hydrocarbon product stream. In such an aspect,any convenient pH monitoring device can be utilized. Further in suchaspects, the pH mentoring device may be in communication with theammonia injection system to meter the appropriate amount of ammonia intothe water wash stream.

In certain aspects, the ammoniated water wash system can be a one stageor two stage process. For instance, in one aspect, the liquidhydrocarbon product stream can be exposed to a single ammoniated waterwash stream and subsequently separated, e.g., via a coalescer, and thenproceed to downstream processing. In an alternative aspect, the liquidhydrocarbon product stream can be exposed to a first ammoniated waterwash stream and subsequently separated, e.g., via a coalescer, followedby exposure to a second ammoniated water wash stream, separated, andthen the treated hydrocarbon product stream can proceed to downstreamprocessing.

Example Ammoniated Water Wash System

FIG. 1 depicts one example system 100 for removing organic acids from aliquid hydrocarbon product stream. The system 100 includes a waterinjection system 110, an ammonia injection system 120, and a coalescer130. In certain aspects, the water injection system 110 includes a waterwash tank 112 and a pump 114. In the aspect depicted in FIG. 1, ammoniafrom the ammonia injection system 120 mixes with the water wash upstreamof the pump 114, and the pump 114 can inject the ammonia-containingwater wash into the hydrocarbon product stream, e.g., a de-ethanizerfeed 140, at a position 142 downstream of the pump 114. In such aspects,the mixture of the ammoniated water wash and de-ethanizer feed 140 issent to the coalescer 130 to separate the de-ethanizer feed 140 from thewater wash. The coalescer 130 can be any convenient type of coalescer.In aspects, as discussed above, the ammonia in the water wash aids insolubilizing the organic acids from the de-ethanizer feed into theaqueous phase (e.g., the water wash). The coalescer 130 can separate ahydrocarbon phase (for eventual introduction into the de-ethanizer) fromthe aqueous phase created by introduction of the water wash. The aqueousphase can include the majority the organic acids that were originallypresent in the de-ethanizer feed. In such aspects, the hydrocarbon phaseexits the coalescer 130 and is sent to the d-eethanizer, while the waterwash, ammonia, and organic acids, can exit the coalescer 130 and befurther processed, e.g. in order to re-use the water for further waterwashing. In aspects, the water stream that exits the coalescer 130 canbe monitored, e.g., with a pH monitoring device 150, to determine thelevel of organic acid removal from the de-ethanizer feed 140.

As discussed above, the pH of the water stream separated from thehydrocarbon phase can be monitored to ensure the appropriate amount oforganic acids are being removed from the liquid hydrocarbon product. Insuch aspects, the pH monitoring device 150 can be in communication witha motor 122 in order to inject the appropriate amount of ammonia intothe water wash system. Any convenient pH monitoring device can beutilized in the system 100 described herein.

As described above, in certain aspects, the liquid hydrocarbon productstream can be exposed to a two stage ammoniated water wash. In such anaspect, a second coalescer (not shown) may be utilized to separate thewater wash from the liquid hydrocarbon product stream. Further, in suchan aspect, the separated water wash can be processed for re-use in thesystem.

Example 1—Simulated One and Two Stage Water Wash of Liquid HydrocarbonProduct Stream

A system similar to that described in FIG. 1, absent the ammoniainjection system, was utilized to model water washing of a de-ethanizerfeed to determine acid removal. Prior to this modeling, a commercialmodel was utilized to estimate the concentrations of acetic acid andpropionic acid in a separator liquid stream or de-ethanizer feed, andwas determined to be between 73-88 ppmw of acetic acid and 48-56 ppmwfor propionic acid. A MTG system producing at about 13,500 barrels perday was used in the modeling.

In the modeling, various wash water rates were injected into thede-ethanizer feed without ammonia and a commercial system was used tomodel the amount of acid taken up by the water phase verses thehydrocarbon phase.

In data not shown, it was estimated that it would take approximately 400gallons per minute (gpm) of water injection (without ammonia) to reducethe acetic acid concentration by 90%.

In additional data not shown, modeling was also conducted on a two stagewater wash system. While the wash water requirements are significantlyreduced when compared to the one stage water wash system, high waterrates are still required to reduce the acid concentration of thede-ethanizer feed stream in this two stage system. For instance, in datanot shown, while 90% acetic acid extraction is possible at a 100 gpmwater rate, 200 gpm is needed to extract the same level of propionicacid compared to the single stage case.

Example 2—Simulated Ammoniated Water Wash of Liquid Hydrocarbon ProductStream at Varying Ammonia Levels

In this Example 2, the system and modeling parameters used above werealso used in this Example 2, except that this Example 2 includeinjecting various amounts of ammonia into the water wash.

FIG. 2 depicts a plot of the water wash rates versus the amount of acidrecovered in the water with an ammonia injection rate of five pounds perhour. As can be seen in FIG. 2, water wash rates of 100 gpm are requiredto achieve an approximately 90% recovery of acetic acid in the waterwash, where even at 100 gpm less than 60% recovery of propionic acid wasachieved. In this particular model and example of FIG. 2, the molarratio of ammonia to the combined amount of acetic acid and propionicacid is approximately 0.7:1.

FIG. 3 depicts a plot of the water wash rates versus the amount of acidrecovered in the water with an ammonia injection rate of seven poundsper hour. As can be seen in FIG. 3, the injection of seven pounds perhour of ammonia at a water wash rate of approximately 25 gpm resulted inapproximately a 90% acetic acid recovery in the water wash. However,only approximately about 60% recovery of propionic acid was obtained atthe 25 gpm water wash rate. In this particular model and example of FIG.3, the molar ratio of ammonia to the acetic acid and propionic acid isapproximately 1:1.

FIG. 4 depicts a plot of the water wash rates versus the amount of acidrecovered in the water with an ammonia injection rate of ten pounds perhour. As can be seen in FIG. 4, unexpectedly, the injection of tenpounds per hour of ammonia at a water wash rate of approximately 10 gpmresulted in over a 99% recovery of acetic acid and over 95% recovery ofpropionic acid in the water wash. In this particular model and exampleof FIG. 4, the molar ratio of ammonia to the acetic acid and propionicacid is approximately 1.5:1.

FIG. 5 depicts a plot of the water wash rates versus the amount of acidrecovered in the water with an ammonia injection rate of twelve poundsper hour. As can be seen in FIG. 5, the injection of twelve pounds perhour of ammonia at a water wash rate of approximately 10 gpm resulted inover a 99.6% recovery of acetic acid and over 98% recovery of propionicacid in the water wash. In this particular model and example of FIG. 5,the molar ratio of ammonia to the acetic acid and propionic acid isapproximately 1.8:1.

As can be seen in FIGS. 4 and 5, with ten and twelve pounds per hour ofammonia, respectively, and a water wash rate of approximately 20-30 gpm,there is a more gradual increase in the amount of acid recovery,compared to between 10-20 gpm water wash rate.

Overall, the results above show that as little as 10-20 gpm of washwater could be employed to extract over 95% of the acetic and propionicacid present in the deethanizer feed, which would greatly reduce thecorrosivity of the finished light gasoline product when ten to twelvepounds per hour of ammonia is injected into the water wash stream. Thedata from these Examples also shows that maintaining the proper ammoniadosage is much more important than the wash water injection rate.

Further, sensitivity studies show that at 20 gpm wash water rate with noammonia injection the resulting pH of the waste water stream from thecoalescer would be approximately 3.5. At an ammonia dosing rate of 12lbs/hr the waste water stream pH would be 7.7.

Additional Embodiments Embodiment 1

A method for removing organic acids from a liquid hydrocarbon productstream, comprising: exposing a liquid hydrocarbon product streamcomprising naphtha boiling range compounds, light ends, and 1 ppmw ormore of organic acids to a water wash stream comprising ammonia to forma treated liquid hydrocarbon product stream, an amount of the water washstream being 0.5 L to 20 L per barrel of the liquid hydrocarbon productstream, wherein the water wash comprises a) 4.0 g or more of ammonia perbarrel of the liquid hydrocarbon product stream, b) a ratio of moles ofammonia in the water wash to moles of the organic acids in the liquidhydrocarbon product stream is 1.5 or more, or c) a combination of a) andb).

Embodiment 2

The method of Embodiment 1, wherein the liquid hydrocarbon productstream has a T95 distillation point of 225° C. or less.

Embodiment 3

The method of any of the above embodiments, wherein the naphtha boilingrange compounds comprise a Research Octane Number (RON) of 80 or more(or 90 or more).

Embodiment 4

The method of any of the above embodiments, wherein the liquidhydrocarbon product stream, prior to the exposing, further comprises 10ppmw to 3000 ppmw of water.

Embodiment 5

The method of any of the above embodiments, wherein the liquidhydrocarbon product stream comprises 1 ppmw to 500 ppmw of the organicacids.

Embodiment 6

The method of any of the above embodiments, further comprising,subsequent to the exposing, separating the water wash stream from thetreated liquid hydrocarbon product stream to form a separated water washstream.

Embodiment 7

The method of Embodiment 6, wherein the separated water wash streamcomprises a pH of 5.5 or more (or 6.0 or more, or 7.0 or more).

Embodiment 8

The method of any of the above embodiments, wherein the water washcomprises 7.5 g or more of ammonia per barrel of hydrocarbon liquidproduct.

Embodiment 9

The method of any of the above embodiments, i) wherein the organic acidscomprise organic acids having 5 carbon atoms or less; ii) wherein theorganic acids comprise formic acid, acetic acid, propionic acid, butyricacid, or a combination thereof;

or iii) a combination of i) and ii).

Embodiment 10

The method of any of the above embodiments, further comprisingseparating at least a portion of the C²⁻ hydrocarbons from the treatedliquid hydrocarbon product stream.

Embodiment 11

The method of Embodiment 10, wherein the separating at least a portionof the C²⁻ hydrocarbons from the treated liquid hydrocarbon productstream comprises exposing the treated liquid hydrocarbon product streamto a de-ethanizer.

Embodiment 12

The method of any of the above embodiments, further comprising, prior tothe exposing the liquid hydrocarbon product stream to the water washstream comprising ammonia, converting one more oxygenates to anintermediate product stream; and separating at least a portion of waterand gas from the intermediate product stream to form the liquidhydrocarbon product stream.

Embodiment 13

The method of any of the above embodiments, wherein the liquidhydrocarbon product stream is derived from an oxygenate conversionprocess.

Embodiment 14

The method of any of the above embodiments, wherein the liquidhydrocarbon product stream comprises 10 ppmw or more of the organicacids, or 50 ppmw or more.

Embodiment 15

A treated liquid hydrocarbon product stream according to the method ofany of Embodiments 1-14.

Although the present invention has been described in terms of specificembodiments, it is not so limited. Suitable alterations/modificationsfor operation under specific conditions should be apparent to thoseskilled in the art. It is therefore intended that the following claimsbe interpreted as covering all such alterations/modifications as fallwithin the true spirit/scope of the invention.

1. A method for removing organic acids from a liquid hydrocarbon productstream, comprising: exposing a liquid hydrocarbon product streamcomprising naphtha boiling range compounds, light ends, and 1 ppmw ormore of organic acids to a water wash stream comprising ammonia to forma treated liquid hydrocarbon product stream, an amount of the water washstream being 0.5 L to 20 L per barrel of the liquid hydrocarbon productstream, the water wash comprising 4.0 g or more of ammonia per barrel ofthe liquid hydrocarbon product stream.
 2. The method of claim 1, whereinthe liquid hydrocarbon product stream has a T95 distillation point of225° C. or less.
 3. The method of claim 1, wherein the naphtha boilingrange compounds comprise a Research Octane Number (RON) of 80 or more.4. The method of claim 1, wherein the liquid hydrocarbon product stream,prior to the exposing, further comprises 10 ppmw to 3000 ppmw of water.5. The method of claim 1, wherein the liquid hydrocarbon product streamcomprises 1 ppmw to 500 ppmw of the organic acids.
 6. The method ofclaim 1, further comprising, subsequent to the exposing, separating thewater wash stream from the treated liquid hydrocarbon product stream toform a separated water wash stream.
 7. The method of claim 6, whereinthe separated water wash stream comprises a pH of 5.5 or more.
 8. Themethod of claim 1, wherein the water wash comprises 7.5 g or more ofammonia per barrel of hydrocarbon liquid product.
 9. The method of claim1, i) wherein the organic acids comprise organic acids having 5 carbonatoms or less; ii) wherein the organic acids comprise formic acid,acetic acid, propionic acid, butyric acid, or a combination thereof; oriii) a combination of i) and ii).
 10. The method of claim 1, wherein aratio of moles of the ammonia in the water wash to moles of the organicacids in the liquid hydrocarbon product stream is 1.5 or more.
 11. Themethod of claim 1, further comprising separating at least a portion ofthe C²⁻ hydrocarbons from the treated liquid hydrocarbon product stream.12. The method of claim 11, wherein the separating at least a portion ofthe C²⁻ hydrocarbons from the treated liquid hydrocarbon product streamcomprises exposing the treated liquid hydrocarbon product stream to ade-ethanizer.
 13. The method of claim 1, further comprising, prior tothe exposing the liquid hydrocarbon product stream to the water washstream comprising ammonia, converting one more oxygenates to anintermediate product stream; and separating at least a portion of waterand gas from the intermediate product stream to form the liquidhydrocarbon product stream.
 14. The method of claim 1, wherein theliquid hydrocarbon product stream is derived from an oxygenateconversion process.
 15. A method for removing organic acids from aliquid hydrocarbon product stream, comprising: exposing a liquidhydrocarbon product stream comprising naphtha boiling range compounds,light ends, and 1 ppmw or more of organic acids to a water wash streamcomprising ammonia to form a treated liquid hydrocarbon product stream,wherein the water wash stream is present in an amount of 0.5 L to 20 Lper barrel of the liquid hydrocarbon product stream, and wherein a ratioof moles of ammonia in the water wash to moles of the organic acids inthe liquid hydrocarbon product stream is 1.5 or more.
 16. The method ofclaim 15, further comprising, subsequent to the exposing, separating thewater wash stream from the treated liquid hydrocarbon product stream toform a separated water wash stream.
 17. The method of claim 16, whereinthe separated water wash stream comprises a pH of 5.5 or more.
 18. Themethod of claim 15, wherein the liquid hydrocarbon product streamcomprises 1 ppmw to 500 ppmw of the organic acids.
 19. The method ofclaim 15, i) wherein the organic acids comprise organic acids having 5carbon atoms or less; ii) wherein the organic acids comprise formicacid, acetic acid, propionic acid, butyric acid, or a combinationthereof; or iii) a combination of i) and ii).
 20. The method of claim15, further comprising separating at least a portion of the C²⁻hydrocarbons from the treated liquid hydrocarbon product stream.